Hair dye composition

ABSTRACT

Provided are a hair bleach composition, hair dye composition and a hair treatment additive having excellent bleaching power, capable of dyeing the hair with a bright and good color, and less damaging to the hair and less irritating to the scalp. 
 
Described specifically, they are a two-part hair bleach composition, which contains (a) a nitrogenous compound represented by the following formula (1) or (2):  
                 
or salt thereof, or (A) a nitrogenous compound having a solubility parameter logP in octanol/water ranging from −1 to 4 and a hydrogen peroxide remaining ratio of from 5 to 90%, or salt thereof, (b) an oxidizing agent, and optionally (c) an alkali agent and, after mixing, has a pH of from 7.5 to 12; a two-part hair dye composition comprising (a) or (A), (b) and (c) and further (d) an oxidation dye or direct dye; and an additive used therefor.

FIELD OF THE INVENTION

The present invention relates to a hair bleach composition and hair dyecomposition, each being less damaging to the hair and less irritating tothe scalp during and after treatment therewith and at the same time,having excellent bleaching power and dyeing power; and an additive to beused for these compositions.

BACKGROUND OF THE INVENTION

For hair bleaching or dyeing, two-part bleaches or permanent hair dyescomposed of a first component part containing an alkali agent and asecond component part containing an oxidizing agent have been usedwidely. The oxidizing agent of the second component part is added inorder to heighten the hair dyeing effect by utilizing the couplingreaction of an intermediate for an oxidation dye and at the same time,cause the hair to turn bright color by promoting oxidative decompositionof melanin granules in the hair. The alkali agent of the first componentpart is added in order to activate the oxidizing agent and therebyenhance the hair dyeing and bleaching effects. Not only to bleach thehair into a lighter color than the original color but also to dye thehair into a color different therefrom, it is necessary to bleach melaninand the other pigments sufficiently. The hair bleaching power usuallydepends on the amounts of the alkali and oxidizing agent. When thecomposition is used for such a purpose, both alkali and oxidizing agentsmust be incorporated in sufficient amounts.

It is the common practice to use ammonia or organic amine as the alkaliagent and hydrogen peroxide as the oxidizing agent. Addition of theseagents in a large amount to obtain necessary bleaching power, however,tends to cause damage to the hair or irritate the scalp, depending ontheir using amount.

As a conventional method for overcoming the above-described problem,provided are the use of 1,3-propanediamine (Japanese Patent Laid-OpenNo. Hei 5-246827), use of triazacyclononane (Japanese Patent Laid-OpenNo. 2002-255763), and the like. They however include the problem that ina mixture system for practical use, they cannot bring about satisfactoryresults in performance.

The present invention therefore provides a hair bleach composition and ahair dye composition, each having an excellent dyeing power, capable ofdyeing the hair into beautiful bright color, and is less damaging to thehair and less irritating to the scalp.

Further, the present invention provides a novel additive to beincorporated for attaining the above-described object.

SUMMARY OF THE INVENTION

In the present invention, there is thus provided a hair bleachcomposition to be used after mixing a first component part containing analkali agent and a second component part containing an oxidizing agent,which comprises, after mixing, the following components (a) to (c):

-   -   (a) a nitrogenous compound represented by the following        formula (1) or (2), or salt thereof:        (wherein, one or two of As each represents CH₂ which may be        substituted by one or two selected from O, S and NH,    -   R¹ represents a hydrogen atom; an alkyl, cycloalkyl or alkenyl        group which has 12 or less carbon atoms and may be substituted        by at least one group selected from a hydroxy group, an amino        group which may be substituted by at least one alkyl group, an        amide group which may be substituted by at least one alkyl        group, a C₁₋₆ (poly)alkoxy or benzyloxy group which may be        substituted by a hydroxy or amino group, a thioether group and        an ester group; an alkyl halide group; or a benzyl,        pyridylmethyl or phenyl group which may be substituted by at        least one halogen atom;    -   R² and R³ each represents a hydrogen atom, an alkyl, alkenyl or        cycloalkyl group which has 12 or less carbon atoms and may be        substituted by at least one group selected from a hydroxy group,        an amino group which may be substituted by at least one alkyl        group and a C₁₋₆ alkoxy group; an acyl group having 12 or less        carbon atoms, an alkylsulfonyl group having 12 or less carbon        atoms, or a phenylsulfonyl group which may be substituted by at        least one alkyl group; or R² and R³ may form a 4- to 7-membered        ring cyclic amino group together with a nitrogen atom adjacent        thereto,    -   R⁴, R⁵ and R⁶ each represents a hydrogen atom; a hydroxy group;        an amino group; an alkyl ether group; or an alkyl or alkenyl        group which has 12 or less carbon atoms and may be substituted        by at least one group selected from a hydroxy group, and an        amino group which may be substituted by at least one alkyl        group,    -   m stands for an integer of from 2 to 5, n stands for an integer        of from 1 to 4 and p stands for an integer of from 2 to 6,    -   (b) an oxidizing agent; and    -   (c) an alkali agent; and after mixing, has a pH of from 7.5 to        12.

In the present invention, there is also provided a hair dye compositionto be used after mixing a first component part containing an alkaliagent and a second component part containing an oxidizing agent, whichcomprises, after mixing, the following components (A) and (b) to (d);

-   -   (A) a nitrogenous compound having a solubility parameter log P        in octanol/water ranging from −1 to 4, and a hydrogen peroxide        remaining ratio ranging from 5 to 90%; or salt of the compound,    -   (b) an oxidizing agent,    -   (c) an alkali agent, and    -   (d) an intermediate for an oxidation dye or a direct dye; and        after mixing, has a pH of from 7.5 to 12.

In the present invention, there is also provided an additive, forattaining an excellent performance, to the above-described hair bleachcomposition or hair dye composition to be used after mixing a firstcomponent part containing an alkali agent and a second component partcontaining an oxidizing agent, which comprises a nitrogenous compoundsatisfying either one of the following conditions:

-   -   (i) a nitrogenous compound represented by the above-described        formula (1) or (2), or salt thereof (condition of chemical        structure), and    -   (ii) a nitrogenous compound having a solubility parameter logP        value in octanol/water ranging from −1 to 4 and a hydrogen        peroxide remaining ratio of from 5 to 90%, or salt thereof        (condition of physical properties).

By satisfying at least one of the above-described conditions relating tophysical properties and chemical structure and thereby causing thealkali agent and oxidizing agent to act efficiently in the hair, theadditive contributes to improvements in bleaching power and hair dyeingpower. Accordingly, without lowering bleaching power and hair dyeingpower, the amounts of the alkali agent and oxidizing agent can bedecreased, leading to alleviation of the hair damage and irritation tothe scalp. In other words, it is possible to improve hair bleaching ordyeing power without increasing the hair damage or irritation to thescalp.

DETAILED DESCRIPTION OF THE INVENTION

The present inventors have found that the above-described problem can beovercome by incorporating, in a hair bleach or a hair dye, a nitrogenouscompound having predetermined physical properties or a nitrogenouscompound having a predetermined structure.

For the nitrogenous compound of the present invention satisfying thecondition of physical properties, the following two requirements arenecessary.

The first requirement is a remaining ratio of hydrogen peroxide. Theremaining ratio of hydrogen peroxide is determined by measuring theremaining amount of hydrogen peroxide in a virtual hair bleachcomposition after a predetermined time. The remaining ratio exceeding apredetermined value allows existence of hydrogen peroxide which can beused for hair bleaching or dyeing and promotes the hair bleachingaction. The remaining ratio below a predetermined value, on the otherhand, prevents excessive stabilization of hydrogen peroxide, whereby theoxidizing agent acts to emit adequate —O₂H (perhydroxy anion). Thehydrogen peroxide remaining ratio in the present invention is from 5% to90%, preferably from 10 to 87%, more preferably 15 to 70% under themeasurement conditions of the hydrogen peroxide remaining ratio whichwill be described later.

Compounds exhibiting a hydrogen peroxide remaining ratio at or above thelower limit 5% can suppress decomposition of hydrogen peroxide servingas an oxidizing agent, while compounds exhibiting a hydrogen peroxideremaining ratio not greater than the upper limit 90% promotes the action(emission of —O₂H or the like) of hydrogen peroxide as an oxidizingagent, which contributes to the appearance of a bleaching effect.

The second requirement is a solubility parameter logP in octanol/water.This is an index of a lipophilicity/hydrophilicity balance of thecompound. More specifically, logP is a distribution ratio of a substancebetween a 1-octanol phase and an aqueous phase at 25° C. and is definedby the following equation:logP=log ((Substance)_(octanol)/(Substance)_(water))(wherein, (Substance)_(octanol) represents a mole concentration of thesubstance in the 1-octanol phase, while (Substance)_(water) represents amole concentration of the substance in the aqueous phase).

The smaller the logP value, the more hydrophilic the substance is. Inthe present invention, this balance is an important factor influencingthe penetration into the hair.

The logP value can be determined by various methods such as measurementand calculation. In this application, utilized was the value “clogP”calculated by a computer soft program which will be described later.

As a result, it has been found that in order to exhibit the effects ofthe present application, the solubility parameter logP must be −1 orgreater but not greater than 4 (from −1 to 4). The logP value ispreferably from −1 to 3, more preferably from −1 to 2.5.

The compound having the logP of −1 or greater penetrates into the hairwell, while that having the logP of 4 or less exhibits good solubilityupon mixing and is not easily separated or precipitated.

Model compounds as described below can be given as the nitrogenouscompounds satisfying the conditions of the present invention. Thepresent invention will next be described based on these model compounds.

In these model compounds, a relationship between structure andperformance as described below is recognized and it will also be anindex for the selection or designing of the nitrogenous compound of thepresent invention.

1. Control of Hydrogen Peroxide Remaining Ratio

In order to cause adequate decomposition of hydrogen peroxide, thecyclic nitrogen in the compound represented by the formula (1) or (2) ispreferably tertiary. More specifically, the compound of the formula (1)or (2) wherein R¹ does not represent a hydrogen atom is preferred, ofwhich the compound of the formula (1) or (2) wherein R¹ represents analkyl or alkenyl group is especially preferred.

The hydrogen peroxide remaining ratio in the present invention ismeasured in the following manner. Measurement of hydrogen peroxideremaining ratio %: In a 50 mL screw tube are charged 20.0 mg of Compound(A) and 5.98 g of deionized water to dissolve the former in the latter.To the resulting solution are added a 2.00 g portion of an aqueous Cusolution obtained by adding deionized water to 26.8 mg of CuCl₂.2H₂O togive a total amount of 100 g, 2.00 g of 15% aqueous ammonia and 10.00 gof 2% aqueous hydrogen peroxide. A magnetic stirrer is put into the tubeand the mixture therein is stirred for 10 minutes in a 30° C. waterbath. Ten minutes later, 0.5 g of the resulting stirred solution isweighed precisely in a 200 mL Erlenmeyer flask with ground-in stopper.After addition thereto of 50 mL of a 10% aqueous solution of sulfuricacid, 10 mL of dichloromethane and 10 mL of a 10% aqueous solution ofpotassium iodide, the mixture is vigorously shaken and then allowed tostand in the dark for about 15 minutes. Then, the reaction mixture istitrated with a 0.02N aqueous solution of sodium thiosulfate. When theyellow color becomes pale during titration, 1 mL of 1% aqueous starch(suspension) is added. The point when a violet color (bluish violet toreddish violet) disappears completely is designated as a terminal pointand hydrogen peroxide % is determined in accordance with thebelow-described equation. The amount of hydrogen peroxide in an aqueoussolution obtained by diluting 10.00 of 2% aqueous hydrogen peroxide with10.00 g of deionized water is also measured and the hydrogen peroxideamount at this time is taken as a hydrogen peroxide remaining ratio of100%. $\text{Hydrogen~~peroxide~~amount~~\%} = {\frac{\begin{matrix}{{Titration}\quad{amount}\quad({mL})} \\{{titer}\quad{of}\quad 0.02\quad N\quad{sodium}\quad{thiosulfate} \times 0.34014}\end{matrix}}{\text{Amount~~of~~stirred~~solution~~weighed~~(mg)}} \times 100}$2. Control of Bleaching Activity

In order to improve bleaching activity, the amino group on the sidechain in the formula (1) is preferably a primary or tertiary one. Inother words, it is preferred that at least one of R² and R³ represents ahydrogen atom, and especially preferred that both represent a hydrogenatom.

3. Control of Solubility Parameter logP

The logP is a balance between hydrophilicity and lipophilicity so thatcompounds may be selected or designed in consideration of its balance inthe whole compound.

Examples of a measure for improving lipophilicity include introductionof a lipophilic group such as hydrocarbon and a reduction in thehydrophilic moiety. More specifically, lipophilicity is improved byintroducing a hydrocarbon group into R⁴, R⁵ and/or R⁶.

Examples of a measure for improving hydrophilicity include introductionof a hetero atom and, in a hydrocarbon atom, substitution of thehydrogen atom of the alkyl group or alkylene group with a group having ahydrophilic moiety such as aminoalkyl group or hydroxy group.

In the present invention, the solubility parameter logP is calculatedusing a computer software program. Calculation of logP: The PartitionCoefficient (Octanol/Water)−ClogP of CS Chem3D ver. 6.0 (product ofCambridge Soft) was used. Instead of salt compounds such as aminehydrochloride or sodium carboxylate salt, the corresponding amine orcarboxylic acid (CO₂H) was input upon calculation.

Examples of the nitrogenous compound or salt thereof capable ofsatisfying the conditions of physical properties, that is, a solubilityparameter logP value in octanol/water ranging from −1 to 4 and ahydrogen peroxide remaining ratio ranging from 5 to 90% include2-aminoethyl-1-methylpyrrolidine, 2-aminomethyl-1-ethylpyrrolidine,2-aminomehtyl-1-butylpyrrolidine,2-aminomethyl-1-hydroxyethylpyrrolidine,2-N-ethylaminomethyl-1-ethylpyrrolidine and1-ethyl-2-(N-hydroxyethyl)aminomethylpyrrolidine.

The logP value and hydrogen peroxide remaining ratio of some compoundsof the present invention capable of satisfying the above-describedconditions are shown in Table 1, together with those of the conventionalart. TABLE 1 Purchased from, or LogP Hydrogen peroxide Compound Namepurity (GC area %) Value remaining ratio Example 2-Aminomethyl-1- 98.6−0.35 85.1 Compound hydroxyethylpyrrolidine2-Aminomethyl-1-methylpyrrolidine 99.4 0.31 63.1 1-Ethyl-2-(N- 99.0 0.6630.5 hydroxyethyl)aminomethylpyrrolidine2-Aminomethyl-1-ethylpyrrolidine 98.8 0.84 43.4 2-N-Ethylaminomethyl-1-99.4 1.53 32.9 ethylpyrrolidine 2-Aminomethyl-1-butylpyrrolidine 98.21.9 45.3 2-Aminomethyl-1- 94.6 2.12 17.0 cyclohexylpyrrolidineComparative Ethylenediaminetetraacetic Wako Pure Chemical −1.93 100Compound acid (2Na salt) Monoethanolamine Wako Pure Chemical −1.3 5.9Diethanolamine Tokyo Kasei −1.46 2.9 1,4,7-Triazacyclononane Tokyo Kasei(3HCl −2.23 96.6 salt) 1,4,7-Trimethyl-1,4,7- Aldrich −1.23 64.8triazacyclononane 1,3-Propanediamine Tokyo Kasei −1.49 19.32-Hydroxy-1,3-propanediamine Tokyo Kasei −2.05 33.6

Based on the above-described finding, it has also been found in theinvention that the compounds represented by the formula (1) or (2), andsalts thereof are also effective for hair bleaching.

In the formulas (1) and (2), A constituting a ring is composedprincipally of —CH₂— and in some cases, it may have, instead of one ortwo —CH₂—, —O—, —S— and/or —NH—.

In the formulas (1) and (2), R¹ represents a hydrogen atom; an alkyl,cycloalkyl, alkenyl, aminoalkyl, hydroxyalkyl, alkoxyalkyl,thioetheralkyl, amide-substituted alkyl or ester-substituted alkylgroup, each having 12 or less, preferably 6 or less carbon atoms; analkyl halide group having 12 or less carbon atoms; a benzyl or phenylgroup which may be substituted by a halogen atom; and a cyclicaminoalkyl group. Examples of the alkyl group having 12 or less carbonatoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl,isobutyl, and isopentyl group. As R¹, preferred is an alkyl or alkenylgroup having 1 to 6 carbon atoms, with methyl, ethyl, butyl orhydroxyethyl group being especially preferred from the viewpoints ofbleaching power·dyeing power.

In the formulas (1) and (2), R² and R³ each represents a hydrogen atom;an alkyl, alkenyl, hydroxyalkyl, aminoalkyl, acyl or alkylsulfonyl grouphaving 12 or less, preferably 1 to 6 carbon atoms; a phenylsulfonylgroup; or a cyclic amino group, of which alkyl, hydroxyalkyl or alkenylgroup having 12 or less carbon atoms is preferred, with a methyl, ethylor hydroxyethyl group being more preferred from the viewpoints ofbleaching power·dyeing power. It is especially preferred that at leastone of R² and R³ represents a hydrogen atom, and most preferred thatboth represent a hydrogen atom.

In the formulas (1) and (2), R⁴, R⁵ and R⁶ each represents a hydrogenatom; a hydroxy group; and an alkyl, alkenyl, hydroxyalkyl or aminoalkylgroup having 12 or less carbon atoms, of which alkyl or alkenyl grouphaving 12 or less, especially 1 to 6 carbon atoms is preferred. Themethyl or ethyl group is especially preferred from the viewpoint of thebleaching power·dyeing power. It is more preferred that any one of R⁴,R⁵ and R⁶ represents a hydrogen atom, and most preferred that R⁶represents a hydrogen atom.

Each functional group will next be described more specifically.

In the formulas (1) and (2), examples of the alkyl or alkenyl grouphaving 12 or less carbon atoms, which is represented by R¹, R², R³, R⁴,R⁵ or R⁶, include methyl, ethyl, propyl, butyl, pentyl, hexyl,isopropyl, isobutyl, isopentyl, vinyl and allyl groups, with methyl andethyl groups being especially preferred from the viewpoint of bleachingpower·dyeing power.

In the formulas (1) and (2) examples of the aminoalkyl group having 12or less carbon atoms, which is represented by R¹, R², R³, R⁴, R⁵ or R⁶,include aminomethyl, aminoethyl, aminopropyl, aminobutyl, aminopentyland aminohexyl groups, with aminomethyl, aminoethyl and aminopropylgroups are preferred.

In the formulas (1) and (2), the poly(alkoxy) group represented by R¹means a polyalkoxy group to which an alkoxy or alkyleneoxide has beenlinked.

In the formulas (1) and (2), examples of the acyl group having 12 orless carbon atoms, which is represented by R² or R³, include formyl,acetyl, propionyl, butanoyl, pentanoyl and hexanoyl groups, with acetyland propionyl groups being especially preferred.

In the formulas (1) and (2), examples of the alkylsulfonyl group having12 or less carbon atoms, which is represented by R² or R³, includemethanesulfonyl and ethanesulfonyl groups.

In the formulas (1) and (2), examples of the phenylsulfonyl group whichmay be substituted by an alkyl group, which is represented by R² or R³,include phenylsulfonyl and tosyl groups.

In the formulas (1) and (2), examples of the 4- to 7-membered ringcyclic amino group which may be formed by coupling of R² and R³ includepyrrolidinyl, piperidino and piperazinyl groups.

In the formulas (1) and (2), examples of the amino group which may besubstituted by at least one alkyl group having 12 or less carbon atoms,which is represented by R¹, R², R³ or R⁴, include amino, methylamino,dimethylamine, ethylamino and diethylamino groups.

In the formulas (1) and (2), examples of the C₁₋₆ alkoxy group which maybe substituted for an alkyl group as R¹ having 12 or less carbon atomsinclude methoxy, ethoxy, propyloxy, isopropyloxy and butoxy groups, ofwhich methoxy) and ethoxy groups are preferred.

In the formulas (1) and (2), examples of the benzyl group as R¹ whichmay be substituted by a halogen atom include benzyl, chlorobenzyl,bromobenzyl and dichorobenzyl groups, with benzyl group being especiallypreferred. Examples of the phenyl group which may be substituted by ahalogen atom include phenyl, chlorophenyl, bromophenyl anddichlorophenyl groups, with a phenyl group being especially preferred.

In the formulas (1) and (2), the integer m is preferably 2 to 4, with 3being especially preferred. The integer n stands for 1 to 4, of which 1or 2 is preferred and 1 is especially preferred. The integer p isespecially preferred from the viewpoint of bleaching power dyeing powerwhen it stands for 2 or 3.

In one preferred embodiment of the present invention, a compoundeffective for hair bleaching is a cyclic amine compound represented bythe following formula (1a) or (2a):

(wherein, R¹ represents a hydrogen atom; an alkyl, cycloalkyl or alkenylgroup which has 12 or less carbon atoms and may be substituted by atleast one group selected from a hydroxy group, an amino group which maybe substituted by at least one alkyl group, an amide group which may besubstituted by at least one alkyl group, a C₁₋₆ (poly)alkoxy orbenzyloxy group which may be substituted by a hydroxy or amino group, athioether group and an ester group; an alkyl halide group, or a benzyl,pyridylmethyl or phenyl group which may be substituted by at least onehalogen atom;

-   -   R² and R³ each represents a hydrogen atom, a C₁₋₆ alkyl group        which may substituted by an amino group which may be substituted        by at least one hydroxy or alkyl group; a C₁₋₆ acyl group; a        C₁₋₆ alkylsulfonyl group; or a phenylsulfonyl group which may be        substituted by an alkyl group; or R² and R³ may form a 4- to        7-membered ring cyclic amino group together with a nitrogen atom        adjacent thereto,    -   R⁴ represents a hydrogen atom; or a C₁₋₆ alkyl group which may        be substituted by an amino group which may be substituted by at        least one hydroxy or alkyl group,    -   m stands for an integer of from 2 to 5, n stands for an integer        of from 1 to 4 and p stands for an integer of from 2 to 6).

These cyclic amine compounds (1a) and (2a) are known compounds and canbe prepared, for example, by the process as described in Japanese PatentPublication No. Sho 46-37589, Japanese Patent Publication No. Sho48-13551, Japanese Patent Publication No. Sho 49-24067, Japanese PatentPublication No. Sho 54-7792, Japanese Patent Publication No. Sho46-27457, Japanese Patent Publication No. Sho 60-56706, InternationalPublication No. 87/07271 pamphlet, and Japanese Patent Publication No.Hei 7-103098.

The cyclic amine compound (1a) may be in the form of an optically active(S) form or (R) form, or any mixture thereof. The cyclic amine compound(2a) may be any diastereomer or a mixture thereof at any ratio. Specificexamples of the cyclic amine compounds (1a) and (2a) will next be shown.

In another preferred embodiment of the present invention, a compoundeffective for hair bleaching is a 2-aminomethylpyrrolidine derivativerepresented by the following formula (1b):

(in the formula (1b), R¹ and R² each represents a C₁₋₆ alkyl or C₃₋₆cycloalkyl group which may be substituted by at least one group selectedfrom hydroxy group, tertiary amino groups and C₁₋₆ alkoxy groups).

The above-described 2-aminomethylpyrrolidine derivative is a novelcompound. The compound can be prepared, for example, in the followingmanner:

A proline derivative represented by the following formula (3):

(in the formula (3), two R¹s may be the same or different and eachrepresents a C₁₋₆ alkyl or C₃₋₆ cycloalkyl group which may besubstituted by at least one group selected from hydroxy group, tertiaryamino groups and C₁₋₆ alkoxy groups) is caused to react with a primaryamine compound represented by the following formula (4):H₂N—R²  (4)(in the formula (4), R² represents a C₁₋₆ alkyl or C₃₋₆ cycloalkyl groupwhich may be substituted by at least one group selected from hydroxygroup, tertiary amino groups and C₁₋₆ alkoxy groups) to obtain anamidated proline derivative represented by the following formula (5):

(in the formula (5), R¹ and R² each has the same meaning as describedabove), followed by reduction of the amide group with a reducing agent.

In the amidation step, the primary amine (4) is used in an amountranging from 0.5 to 20 equivalents relative to the raw material prolinederivative (4). As a catalyst, alcoholate such as sodium methoxide(NaOMe), iodine ion such as sodium iodide and cyan ion such as sodiumcyanide may be added. As the reaction solvent, solvents ordinarilyemployed in organic synthesis, for example, an alcohol solvent such asmethanol, halogen solvent such as chloroform, aromatic solvent such asbenzene, ether solvent such as diethyl ether, hydrocarbon solvent suchas hexane, acetonitrile, DMF, DMSO, N-methylpyrrolidone or water, ormixture thereof may be used. The reaction can be effected within atemperature range of from 0 to 220° C. The reaction is usually carriedout under normal pressure.

In the reduction step, a hydrogenation reagent may be used as thereducing agent. Examples include LiAlH₄ and NaAlH₄. The amount of thehydrogenation reagent falls within a range of from 0.5 to 20 equivalentsrelative to the amidated proline derivative represented by the formula(5). The reduction is conducted in an inert solvent, for example, anaromatic solvent such as benzene, an ether solvent such as diethylether, or hydrocarbon solvent such as hexane. The reaction is effectedwithin a range of from −20° C. to reflux temperature.

The aminomethylpyrrolidine derivative (1b) has at least one asymmetrichydrocarbon. Each asymmetric hydrocarbon may be an optically activesubstance or racemic body, or a mixture thereof at any ratio. In view ofa production cost, a racemic body or a mixture of diastereomers at anyratio is preferred.

Specific examples of the aminomethylpyrrolidine derivative (1b) includethe compounds represented by the following chemical structures:

Preferred examples of the salt of the nitrogenous compound (Compound (1)or (2)) of the formula (1) or (2) include salts of an inorganic acid ororganic acid such as hydrochloric acid, sulfuric acid, phosphoric acid,acetic acid, propionic acid, lactic acid, citric acid, succinic acid,hydrobromic acid, hydroiodic acid, methanesulfonic acid and perchloricacid.

As the compound (1) or (2) serving as component (a), two or morecompounds may be used in combination and their content is notparticularly limited. From the viewpoints of sufficient bleaching·hairdyeing effects, the content is preferably from 0.01 to 20 wt. %, morepreferably from 0.02 to 10 wt. %, still more preferably from 0.05 to 8wt. %, especially preferably from 0.1 to 5 wt. % in the wholecomposition composed of the first component part and the secondcomponent part.

As the oxidizing agent serving as Component (b), hydrogen peroxide andhydrogen peroxide generators such as urea peroxide, melamine peroxide,sodium perborate, potassium perborate, sodium percarbonate and potassiumpercarbonate can be given as examples, of which hydrogen peroxide isespecially preferred. Its using amount can be selected as needed insofaras it does not cause the pH to exceed the required range. For example,from the viewpoints of sufficient bleaching hair dyeing effects, andreduction of the hair damage or scalp irritation, the content of theoxidizing agent in terms of hydrogen peroxide is preferably from 0.1 to12 wt. %, more preferably from 0.5 to 9 wt. %, especially preferablyfrom 1 to 6 wt. % in the whole composition having the first and secondcomponent parts.

Examples of the alkali agent as the component (c) include ammonia,alkanolamines such as monoethanolamine, isopropanolamine,2-amino-2-methylpropanol and 2-aminobutanol, alkanediamines such as1,3-propanediamine, and carbonates such as ammonium carbonate, ammoniumbicarbonate, guanidine carbonate, sodium carbonate, potassium carbonate,sodium bicarbonate and potassium bicarbonate. Of these, ammonia andalkanolamines are preferred. Of the alkanolamines, monoethanolamine ismore preferred. As the alkali agent, two or more of the above-describedones may be used in combination. Its content can be selected as neededwithin a range satisfying the necessary pH. From the standpoints ofproviding sufficient bleaching·dyeing effect and also reducing hairdamage and irritation to the scalp, the content of the alkali agent ispreferably from 0.05 to 10 wt. %, more preferably from 0.1 to 5 wt. %,especially preferably from 0.2 to 3 wt. % in the whole compositioncomposed of the first component part and the second component part.

The hair bleach composition or hair dye composition according to thepresent invention can bring about sufficient bleaching·dyeing effectswithout using ammonia as an alkali agent. Without any ammonia-derivedirritating odor and unpleasant feeling during use, the composition ispreferably employed.

In the hair bleach composition or hair dye composition of the presentinvention, a first component part containing an alkali agent and asecond component part containing an oxidizing agent are mixed at a ratioranging from 1:0.5 to 1:3 in terms of first component part:secondcomponent part (weight ratio) in consideration of practical utility.

The first component part and the second component part preferably have apH of from 8 to 12 and from 2 to 5, respectively, at 25° C. The hair dyecomposition after mixture of the first and second component parts has apH of from 7.5 to 12, but in view of the bleaching·hair dyeing effectsand reduction in the skin irritation, the pH from 8 to 11 is preferred.As a pH regulator, in addition to the alkali agent as Component (c), aninorganic acid such as hydrochloric acid or phosphoric acid, an organicacid such as citric acid, glycolic acid or lactic acid, a hydrochloridesalt such as ammonium chloride or monoethanolamine hydrochloride, orphosphate salt such as monopotassium dihydrogenphosphate or disodiummonohydrogen phosphate can be used.

When the hair bleach composition or hair dye composition of the presentinvention further contains, as a chelating agent which is known to beused for hair bleaching and hair dye compositions, at least one selectedfrom ethylenediaminetetraacetic acid,ethylenediaminehydroxyethyltriacetic acid, diethylenetriaminepentaaceticacid and salts thereof, the oxidizing agent and alkali agent act in thehair more efficiently. Addition of the chelating agent is thereforepreferred. The content of the chelating agent preferably falls within arange of from 0.01 to 5 wt. % in the whole composition composed of thefirst component and second component parts from the viewpoints ofsufficient bleaching hair dyeing effects. The chelating agent can beincorporated in either one or both of the first and second componentparts.

For the hair bleach or hair dye composition of the present invention,water and/or organic solvent is used as a medium. Examples of theorganic solvent include lower alkanols such as ethanol and 2-propanol,aromatic alcohols such as benzyl alcohol and benzyloxyethanol, polyolssuch as propylene glycol, 1,3-butanediol, diethylene glycol andglycerin, cellosolves such as ethyl cellosolve, butyl cellosolve andbenzyl cellosolve, and carbitols such as ethyl carbitol and butylcarbitol.

The hair dye composition of the present invention further contains, asComponent (d), an intermediate for oxidation dye or a direct dye.

As such an intermediate for oxidation dye, known developers and couplerswhich are ordinarily employed for hair dyes can be used. Examples of thedeveloper include paraphenylenediamine, toluene-2,5-diamine,2-chloro-paraphenylenediamine, N-methoxyethyl-paraphenylenediamine,N,N-bis(2-hydroxyethyl)-paraphenylenediamine,2-(2-hydroxyethyl)-paraphenylenediamine,2,6-dimethyl-para-phenylenediamine, 4,4′-diaminodiphenylamine,1,3-bis(N-(2-hydroxyethyl)-N-(4-aminophenyl)amino)-2-propanol,PEG-3,2,2′-paraphenylenediamine, paraminophenol, paramethylaminophenol,3-methyl-4-aminophenol, 2-aminomethyl-4-aminophenol,2-(2-hydroxyethylaminomethyl)-4-aminophenol, orthoaminophenol,2-amino-5-methylphenol, 2-amino-6-methylphenol,2-amino-5-acetamidophenol, 3,4-diaminobenzoic acid, 5-aminosalicylicacid, 2,4,5,6-tetraminopyrimidine, 2,5,6-triamino-4-hydroxypyrimidine,4,5-diamino-1-(4′-chlorobenzyl)pyrazole and4,5-diamino-1-hydroxyethylpyrazole, and salts thereof.

Examples of the coupler include metaphenylenediamine,2,4-diaminophenoxyethanol, 2-amino-4-(2-hydroxyethylamino)anisole,2,4-diamino-5-methylphenetole, 2,4-diamino-5-(2-hydroxyethoxy)toluene,2,4-dimethoxy-1,3-diaminobenzene, 2,6-bis(2-hydroxyethylamino)toluene,2,4-diamino-5-fluorotoluene, 1,3-bis(2,4-diaminophenoxy)propane,metaminophenol, 2-methyl-5-aminophenol,2-methyl-5-(2-hydroxyethylamino)phenol, 2,4-dichloro-3-aminophenol,2-chloro-3-amino-6-methylphenol, 2-methyl-4-chloro-5-aminophenol,N-cyclopentyl-metaaminophenol,2-methyl-4-methoxy-5-(2-hydroxyethylamino)phenol,2-methyl-4-fluoro-5-aminophenol, resorcin, 2-methylresorcin,4-chlororesorcin, 1-naphthol, 1,5-dihydroxynaphthalene,1,7-dihydroxynaphthalene, 2,7-dihydroxynaphthalene,2-isopropyl-5-methylphenol, 4-hydroxyindole, 5-hydroxyindole,6-hydroxyindole, 7-hydroxyindole, 6-hydroxybenzomorpholine,3,4-methylenedioxyphenol, 2-bromo-4,5-methylenedioxyphenol,3,4-methylenedioxyaniline,1-(2-hydroxyethyl)amino-3,4-methylenedioxybenzene,2,6-dihydroxy-3,4-dimethylpyridine, 2,6-dimethoxy-3,5-diaminopyridine,2,3-diamino-6-methoxypyridine, 2-methylamino-3-amino-6-methoxypyridine,2-amino-3-hydroxypyridine, and 2,6-diaminopyridine and salts thereof.

As each of the developer and coupler, they may be used in combination oftwo or more thereof. The content of the developer or coupler ispreferably from 0.01 to 5 wt. %, especially preferably from 0.1 to 4 wt.% in the whole composition composed of first component and secondcomponent parts.

As the direct dye, on the other hand, known acidic dyes, basic dyes,disperse dyes, reactive dyes and the like, which can be used for hairdyes, can be used. The acidic dyes include Red No. 2 (C.I. 16185), RedNo. 3 (C.I. 45430), Red No. 102 (C.I. 16255), Red No. 104 (1) (C.I.45410), Red No. 105 (1) (C.I. 45440), Red No. 106 (C.I. 45100), YellowNo. 4 (C.I. 19140), Yellow No. 5 (C.I. 15985), Green No. 3 (C.I. 42053),Blue No. 1 (C.I. 42090), Blue No. 2 (C.I. 73015), Red No. 201 (C.I.15850), Red No. 227 (C.I. 17200), Red No. 230 (1) (C.I. 45380), Red No.231 (C.I. 45410), Red No. 232 (C.I. 45440), Orange No. 205 (C.I. 15510),Orange No. 207 (C.I. 45425), Yellow No. 202 (1) (C.I. 45350), Yellow No.203 (C.I. 47005), Green No. 201 (C.I. 61570), Green No. 204 (C.I.59040), Green No. 205 (C.I. 42095), Blue No. 202 (C.I. 42052), Blue No.205 (C.I. 42090), Brown No. 201 (C.I. 20170), Red No. 401 (C.I. 45190),Red No. 502 (C.I. 16155), Red No. 503 (C.I. 16150), Red No. 504 (C.I.14700), Red No. 506 (C.I. 15620), Orange No. 402 (C.I. 14600), YellowNo. 402 (C.I. 18950), Yellow No. 403 (1) (C.I. 10316), Yellow No. 406(C.I. 13065), Yellow No. 407 (C.I. 18820), Green No. 401 (C.I. 10020),Green No. 402 (C.I. 42085), Violet No. 401 (C.I. 60730), Black No. 401(C.I. 20470), Acid Black 52 (C.I. 15711), Acid Blue 1 (C.I. 42045), AcidBlue 3 (C.I. 42051), Acid Blue 62 (C.I. 62045), Acid Brown 13 (C.I.10410), Acid Green 50 (C.I. 44090), Acid Orange 3 (C.I. 10385), AcidOrange 6 (C.I. 14270), Acid Red 14 (C.I. 14720), Acid Red 35 (C.I.18065), Acid Red 73 (C.I. 27290), Acid Red 184 (C.I. 15685), andBrilliant Black 1 (C.I. 28440).

The basic dyes include Basic Blue 7 (C.I. 42595), Basic Black 16 (C.I.12210), Basic Blue 22 (C.I. 61512), Basic Blue 26 (C.I. 44045), BasicBlue 99 (C.I. 56059), Basic Blue 117, Basic Violet 10 (C.I. 45170),Basic Violet 14 (C.I. 42515), Basic Brown 16 (C.I. 12250), Basic Brown17 (C.I. 12251), Basic Red 2 (C.I. 50240), Basic Red 12 (C.I. 48070),Basic Red 22 (C.I. 11055), Basic Red 51, Basic Red 76 (C.I. 12245),Basic Red 118 (C.I. 12251:1), Basic Orange 31, Basic Yellow 28 (C.I.48054), Basic Yellow 57 (C.I. 12719), Basic Yellow 87 and Basic Black 2(C.I. 11825); basic dyes each having a quaternized nitrogen atom on aside chain of an aromatic ring as described in Japanese PatentPublication No. Sho 58-2204, Japanese Patent Application Laid-Open No.Hei 9-118832 and the like; and basic dyes as described in JapaneseLanguage Laid-open Publication (PCT) No. Hei 10-502946, Japanese PatentApplication Laid-Open No. Hei 10-182379, Japanese Patent ApplicationLaid-Open No. Hei 11-349457 and the like.

Examples of direct dyes other than acidic dyes or basic dyes include2-amino-3-nitrophenol, 2-amino-4-nitrophenol, 2-amino-5-nitrophenol,4-amino-3-nitrophenol, 2-amino-6-chloro-4-nitrophenol,4-hydroxypropylamino-3-nitrophenol,3-nitro-para-hydroxyethylaminophenol, 2-nitro-para-phenylenediamine,4-nitro-ortho-phenylenediamine, 4-nitro-meta-phenylenediamine,6-nitro-ortho-toludine, 6-nitro-para-toluidine,hydroxyethyl-2-nitro-para-toluidine,N,N′-bis(2-hydroxyethyl)-2-nitro-para-phenylenediamine,2-chloro-5-nitro-N-hydroxyethyl-para-phenylenediamine,2-nitro-5-glycerylmethylaniline, 3-methylamino-4-nitrophenoxyethanol,N-ethyl-3-nitroPABA, picramic acid, 2-hydroxyethylpicramic acid,4-nitrophenylaminoethylurea, Violet No. 201 (C.I. 60725), Solvent Yellow44 (C.I. 56200), Disperse Red 17 (C.I. 11210), Disperse Violet 1 (C.I.61100), Disperse Violet 4 (C.I. 61105), Disperse Blue 3 (C.I. 61505),Disperse Blue 7 (C.I. 62500), HC Blue No. 2, HC Blue No. 8, HC OrangeNo. 1, HC Orange No. 2, HC Red No. 1, HC Red No. 3, HC Red No. 7, HC RedNo. 8, HC Red No. 10, HC Red No. 11, HC Red No. 13, HC Red No. 16, HCViolet No. 2, HC Yellow No. 2, HC Yellow No. 5, HC Yellow No. 6, HCYellow No. 7, HC Yellow No. 9, and HC Yellow No. 12.

These direct dyes may be used in combination of two or more thereof. Itscontent is preferably from 0.001 to 5 wt. %, especially preferably from0.01 to 4 wt. % in the whole composition composed of the first componentand second component parts. The oxidation dye and direct dye may be usedin combination.

To the hair bleach composition or hair dye composition according to thepresent invention, ingredients commonly employed as cosmetic rawmaterials can be added, in addition to the above-described ingredients.Illustrative of such optional ingredients are hydrocarbons, animal orvegetable oils and fats, higher fatty acids, penetration enhancers,cationic surfactants, natural or synthetic polymers, higher alcohols,ethers, amphoteric surfactants, nonionic surfactants, proteinderivatives, amino acids, antiseptics, chelating agents, stabilizers,antioxidants, plant extracts, crude drug extracts, vitamins, colorants,fragrances and ultraviolet absorbers.

The hair bleach composition or hair dye composition of the presentinvention is provided, similar to oxidation type hair bleaches or hairdyes widely employed now, as a two-part type having a first componentpart containing an alkali agent and a second component part containingan oxidizing agent. These first and second component parts can beprovided in the form, for example, of liquid, emulsion, cream, gel,paste, or mousse. It may also be provided in the form of an aerosol. Themixture of the first component part and second component part haspreferably a viscosity enough not to cause sagging when applied to thehair. It preferably has a viscosity of 2000 to 100000 mPa·s whenmeasured at 25° C. by a Brookfield rotating viscometer. The viscosityhere is a value measured after rotation using Rotor No. 3 for 1 minuteat 12 rpm.

In order to bleach or dye the hair by using the hair bleach compositionor hair dye composition of the present invention, it is only necessaryto mix the first component part and second component part of the hairdye composition of the present invention, apply the mixture to the hairat 15 to 45° C., causing it to act on the hair for 1 to 60 minutes,preferably from 3 to 45 minutes, washing the hair and then drying.

EXAMPLES

Compounds used in Examples 1 to 32 are shown below.

Examples 1 to 9 and Comparative Examples 1 and 2

Oxidation type hair bleach compositions as shown in Table 2 wereprepared in a conventional manner. TABLE 2 Comparative Examples Examples1 2 3 4 5 6 7 8 9 1 2 First 28 wt. % Aqueous ammonia 8 8 8 8 8 8 8 8 8 88 comp. Tetrasodium ethylenediaminetetra- 0.125 0.125 0.125 0.125 0.1250.125 0.125 0.125 0.125 0.125 0.125 part acetate 4 hydrate Compound(1-1) 0.4 Compound (1-2) 0.4 Compound (1-3) 0.4 Compound (1-4) 0.4Compound (2-1) 0.4 Compound (1-5) 0.4 Compound (1-6) 0.4 Compound (1-7)0.4 Compound (1-8) 0.4 Purified water Balance Balance Balance BalanceBalance Balance Balance Balance Balance Balance Balance Second 35 wt. %Aqueous hydrogen 17.14 17.14 17.14 17.14 17.14 17.14 17.14 17.14 17.1417.14 25.71 comp. peroxide part Purified water Balance Balance BalanceBalance Balance Balance Balance Balance Balance Balance Balance

After 1 part by weight of the first component part was mixed with 1.5parts of the second component part, the mixture was applied to the blackhair of the Japanese (1 g tress). The mixture was caused to act on thehair for 30 minutes and then the hair was washed with a conventionalshampoo, followed by drying. The color tone of the bleached hair wasmeasured by a calorimeter of Konica Minolta and a difference in the huefrom the untreated hair was observed. As a result, it has been foundthat in Examples 1 to 9, the bleaching property was better than inComparative Example 1 and the bleaching property was comparable to thatof Comparative Example 2. With regards to the touch of the hair aftertreatment, the bleached hair with the composition of Comparative Example2 was damaged severely, but the bleached hair with any one of thecompositions of Examples 1 to 9 was only slightly damaged and its degreewas comparable to that of Comparative Example 1.

Examples 10 to 14 and Comparative Examples 3 to 4

In a conventional manner, oxidation type hair bleach compositions asshown in Table 3 were prepared. TABLE 3 Comparative Examples Examples 1011 12 13 14 3 4 First Monoethanolamine 5 5 5 5 5 5 5 Comp. TetrasodiumEDTA 0 0 0 0 0 0 0 part tetrahydrate Compound (1-1) 0.4 Compound (1-2)0.4 Compound (1-3) 0.4 Compound (1-4) 0.4 Compound (2-1) 0.4 Purifiedwater Balance Balance Balance Balance Balance Balance Balance Second 35wt. % Aqueous 17.14 17.14 17.14 17.14 17.14 17.14 25.71 Comp. hydrogenperoxide part Purified water Balance Balance Balance Balance BalanceBalance Balance

In a similar manner to Examples 1 to 9, bleaching, washing and dryingwere conducted and the color tone of the bleached hair was measured. Adifference in the color hue from the untreated hair was observed. As aresult, the bleaching property of the hair treated with any one of thecompositions in Examples 10 to 14 was superior to that in ComparativeExample 3 and was comparable to that in Comparative Example 4. Withregards to the touch of the hair, the hair bleached with the compositionof Comparative Example 4 was damaged severely, while the damage of thehair treated with any one of the compositions in Examples 10 to 14 wasas week as that treated with the composition obtained in ComparativeExample 3.

Examples 15 to 24

In a conventional manner, oxidation type hair bleach compositions asshown in Tables 4 and 5 were prepared. TABLE 4 Examples 15 16 17 18 19First Compound (1-2) 0.1 2 comp. Compound (1-3) 1 part Compound (1-4) 1Compound (2-1) 1 28 wt. % Aqueous ammonia 6 6 3 Monoethanolamine 5 3 5Propylene glycol 10 10 2 2 2 Ethanol 15 15 Polyoxyethylene (20)octyldodecyl ether 10 10 Polyoxyethylene (40) cetyl ether 2 2 2Polyoxyethylene (2) cetyl ether 2.5 2.5 2.5 Oleic acid diethanolamide 88 Oleyl alcohol 2 2 Stearyl trimethylammonium chloride 1.5 1.5 1.5Cetanol 1 1 1 Liquid paraffin 0.5 0.5 0.5 Ammonium chloride q.s.^(a))q.s.^(a)) q.s.^(a)) q.s.^(a)) q.s.^(a)) Purified water Balance BalanceBalance Balance Balance Second Hydrogen peroxide 6 3 3 6 9 comp.Methylparaben 0.1 0.1 0.1 0.1 0.1 part Phosphoric acid q.s.^(b))q.s.^(b)) q.s.^(b)) q.s.^(b)) q.s.^(b)) Purified water Balance BalanceBalance Balance Balance^(a))amount to adjust the pH to 9.8^(b))amount to adjust the pH to 3.5

TABLE 5 Examples 20 21 22 23 24 First Compound (1-1) 0.1 2 comp.Compound (1-2) 1 part Compound (1-4) 1 Compound (2-1) 0.1 1 Tetrasodium1 0.5 ethylenediaminetetraacetate tetrahydrate Trisodium 2ethylenediaminehydroxyethyltriacetate Pentasodium 1Diethylenetriaminepentaacetate 28 wt. % Aqueous ammonia 6 6 3Monoethanolamine 5 3 5 Propylene glycol 10 10 2 2 2 Ethanol 15 15Polyoxyethylene (20) octyldodecyl ether 10 10 Polyoxyethylene (40) cetylether 2 2 2 Polyoxyethylene (2) cetyl ether 2.5 2.5 2.5 Oleic aciddiethanolamide 8 8 Oleyl alcohol 2 2 Stearyltrimethylammonium chloride1.5 1.5 1.5 Cetanol 1 1 1 Liquid paraffin 0.5 0.5 0.5 Ammonium chlorideq.s.^(a)) q.s.^(a)) q.s.^(a)) q.s.^(a)) q.s.^(a)) Purified water BalanceBalance Balance Balance Balance Second Hydrogen peroxide 6 3 3 6 9 comp.Methyparaben 0.1 0.1 0.1 0.1 0.1 part Phosphoric acid q.s.^(b))q.s.^(b)) q.s.^(b)) q.s.^(b)) q.s.^(b)) Purified water Balance BalanceBalance Balance Balance^(a))amount to adjust the pH to 9.8^(b))amount to adjust the pH to 3.5

In a similar manner to Examples 1 to 9 except for the use of 1 part byweight of the second component part relative to 1 part by weight of thefirst component part, bleaching, washing and drying were conducted. Thecolor tone of the bleached hair was measured and a difference in colorhue from the untreated hair was observed. As a result, the bleachingproperty of the hair treated with any one of the compositions obtainedin Examples 20 to 24 was superior to that of a composition to which anyone of the compounds (1-2), (1-3), (1-4) and (2-1) had not been added.

Examples 25 to 32

In a conventional manner, oxidation type hair dyes as shown in Tables 6and 7 were prepared. TABLE 6 Examples 25 26 27 28 First Compound (1-2)0.1 Comp. Compound (1-3) 1 Part Compound (1-4) 1 Compound (2-1) 0.1 1Tetrasodium ethylenediaminetetraacetate 0.5 tetrahydrate Trisodiumethylenediaminehydroxyethyltriacetate 2 Pentasodiumdiethylenetriaminepentaacetate 1 Toluene-2,5-diamine 1.9 1.9 1Para-aminophenol 1 Resorcin 2 2 Para-aminoorthocresol 1.12,4-Diaminophenoxyethanol 1.37 28 wt. % Aqueous ammonia 5 5 5 5Monoethanolamine 2 2 2 2 Propylene glycol 8 8 8 8 Polyoxyethylene (20)isostearyl ether 24 24 24 24 Polyoxyethylene (2) isostearyl ether 20 2020 20 Merquat (product of Calgon, 35 wt. % aq. soln.) 8 8 Polymer JR400(product of Union Carbide) 0.5 Amodimethicone SM8702C (product of Dow 2Corning Toray Silicone) Sodium sulfite 0.05 0.05 0.05 0.05 Ascorbic acid0.5 0.5 0.5 0.5 Fragrance q.s. q.s. q.s. q.s. Ammonium chloride q.s.^(c)⁾ q.s.^(c)) q.s.^(c) ⁾ q.s.^(c) ⁾ Purified water Balance Balance BalanceBalance Second Hydrogen peroxide 6 3 3 3 comp. Methylparaben 0.5 0.5 0.50.5 part Phosphoric acid q.s.^(d) ⁾ q.s.^(d)) q.s.^(d)) q.s.^(d))Purified water Balance Balance Balance Balance^(a))amount to adjust the pH to 10^(b))amount to adjust the pH to 3.5

TABLE 7 Examples 29 30 31 32 First Compound (1-2) 0.1 Comp. Compound(1-3) 1 Part Compound (1-4) 1 Compound (2-1) 0.1 1 Tetrasodiumethylenediaminetetraacetate 0.5 tetrahydrate Trisodiumethylenediaminehydroxyethyltriacetate 2 PentasodiumDiethylenetriaminepentaacetate 1 Toluene-2,5-diamine 1.9Para-aminophenol 1 Resorcin 2 Para-aminoorthocresol 1.12,4-Diaminophenoxyethanol 1.37 Basic Red 12 0.2 0.2 Basic Red 76 0.1 0.2HC Red 3 0.1 0.2 Monoethanolamine 5 5 5 5 Propylene glycol 8 8 8 8Polyoxyethylene (20) isostearyl ether 24 24 24 24 Polyoxyethylene (2)isostearyl ether 20 20 20 20 Merquat (product of Calgon, 35 wt. % aq.soln.) 8 8 Polymer JR400 (product of Union Carbide) 0.5 AmodimethiconeSM8702C (product of Dow 2 Corning Toray Silicone) Sodium sulfite 0.050.05 0.05 0.05 Ascorbic acid 0.5 0.5 0.5 0.5 Fragrance q.s. q.s. q.s.q.s. Ammonium chloride q.s.^(c)) q.s.^(c)) q.s.^(c)) q.s.^(c)) Purifiedwater Balance Balance Balance Balance Second Hydrogen peroxide 6 3 3 3comp. Methylparaben 0.5 0.5 0.5 0.5 part Phosphoric acid q.s.^(d))q.s.^(d)) q.s.^(d)) q.s.^(d)) Purified water Balance Balance BalanceBalance^(a))amount to adjust the pH to 10^(b))amount to adjust the pH to 3.5

After 1 part by weight of the first component part was mixed with 1.5parts by weight of the second component part, the mixture was applied tothe black hair (1 g) of the Japanese at 30° C. The mixture was allowedto act on the hair for 30 minutes, followed by washing with aconventional shampoo and drying. The color tone of the hair thus dyedwas measured by a calorimeter of Konica Minolta and a difference in thecolor hue from the untreated hair was observed. As a result, the hairtreated with any one of the compositions obtained in Examples 25 to 32was superior to that treated with the composition to which any one ofthe compound (1-2), (1-3), (1-4) and (2-1) had not been added.

Examples 33 to 40 and Comparative Examples 5 and 6

Compounds used in Examples 33 to 40 are shown below:

The oxidation type hair bleach compositions as shown in Table 8 wereprepared. TABLE 8 Examples Comp. Ex. 33 34 35 36 37 38 39 40 5 6 First28 wt. % aqueous ammonia 8 8 8 8 8 8 8 8 8 8 comp. Tetrasodium 0.1250.125 0.125 0.125 0.125 0.125 0.125 0.125 0.125 0.125 partethylenediaminetetraacetate tetrahydrate Compound A 0.4 Compound B 0.4Compound C 0.4 Compound D 0.4 Compound E 0.4 Compound F 0.4 Compound G0.4 Compound H 0.4 Purified water Balance Balance Balance BalanceBalance Balance Balance Balance Balance Balance Second 35 wt. % aqueoushydrogen 17.14 17.14 17.14 17.14 17.14 17.14 17.14 17.14 17.14 25.71comp. peroxide Part Purified water Balance Balance Balance BalanceBalance Balance Balance Balance Balance Balance

After 1 part by weight of the first component part was mixed with 1.5parts by weight of the second component part, the mixture was applied tothe black hair (1 g tress) of the Japanese at 30° C. The mixture wasallowed to act on the hair for 30 minutes, followed by washing with aconventional shampoo and drying. The color tone of the hair thus dyedwas measured by a colorimeter of Konica Minolta and a difference in thecolor hue from the untreated hair was observed. As a result, the hairtreated with any one of the compositions obtained in Examples 33 to 40was superior in bleaching property to that treated with the compositionobtained in Comparative Example 5 and was comparable to ComparativeExample 6.

INDUSTRIAL APPLICABILITY

The hair dye composition of the present invention has excellentbleaching power, is capable of dyeing the hair with a bright color toneand good color hue and is less damaging to the hair and less irritatingto the scalp.

1. A hair bleach composition to be used after mixing a first componentpart containing an alkali agent and a second component part containingan oxidizing agent, which comprises, after mixing, the followingcomponents (a) and (b): (a) a nitrogenous compound represented by thefollowing formula (1) or (2), or salt thereof:

(wherein, one or two of As each represents CH₂ which may be substitutedby one or two selected from O, S and NH, R¹ represents a hydrogen atom;an alkyl, cycloalkyl or alkenyl group which has 12 or less carbon atomsand may be substituted by at least one group selected from a hydroxygroup, an amino group which may be substituted by at least one alkylgroup, an amide group which may be substituted by at least one alkylgroup, a C₁₋₆ (poly)alkoxy or benzyloxy group which may be substitutedby a hydroxy group or an amino group, a thioether group and an estergroup; an alkyl halide group; or a benzyl, pyridylmethyl or phenyl groupwhich may be substituted by at least one halogen atom; R² and R³ eachrepresents a hydrogen atom; an alkyl, alkenyl or cycloalkyl group whichhas 12 or less carbon atoms and may substituted by at least one groupselected from hydroxy group, amino group which may be substituted by atleast one alkyl group and C₁₋₆ alkoxy group; an acyl group having 12 orless carbon atoms; an alkylsulfonyl group having 12 or less carbonatoms; or a phenylsulfonyl group which may be substituted by at leastone alkyl group; or R² and R³ may form a 4- to 7-membered ring cyclicamino group together with a nitrogen atom adjacent thereto, R⁴, R⁵ andR⁶ each represents a hydrogen atom; a hydroxy group; an amino group; analkyl ether group; or an alkyl or alkenyl group which has 12 or lesscarbon atoms and may be substituted by at least one group selected froma hydroxy group, and an amino group which may be substituted by at leastone alkyl group, m stands for an integer of from 2 to 5, n stands for aninteger of from 1 to 4 and p stands for an integer of from 2 to 6, (b)an oxidizing agent; and (c) an alkali agent; and has, after mixing, a pHof from 7.5 to
 12. 2. A hair bleach composition to be used after mixinga first component part containing an alkali agent and a second componentpart containing an oxidizing agent, which comprises, after mixing, thefollowing components (A) and (b): (A) a nitrogenous compound having asolubility parameter logP in octanol/water ranging from −1 to 4, and ahydrogen peroxide remaining ratio from 5 to 90%; or salt of thecompound, and (b) an oxidizing agent; and has, after mixing, a pH offrom 7.5 to
 12. 3. The hair bleach composition of claim 1 or 2, furthercomprising ethylenediaminetetraacetic acid,ethylenediaminehydroxyethyltriacetic acid ordiethylenetriaminepentaacetic acid or salt thereof.
 4. A hair dyecomposition to be used after mixing a first component part containing analkali agent and a second component part containing an oxidizing agent,which comprises, after mixing, comprises the following components (a) to(d): (a) a nitrogenous compound represented by the following formula (1)or (2):

(wherein, one or two of As each represents CH₂ which may be substitutedby one or two selected from O, S and NH, R¹ represents a hydrogen atom;an alkyl, cycloalkyl or alkenyl group which has 12 or less carbon atomsand may be substituted by at least one group selected from a hydroxygroup, an amino group which may be substituted by at least one alkylgroup, an amide group which may be substituted by at least one alkylgroup, a C₁₋₆ (poly)alkoxy or benzyloxy group which may be substitutedby a hydroxy or amino group, a thioether group and an ester group; analkyl halide group; or a benzyl, pyridylmethyl or phenyl group which maybe substituted by at least one halogen atom; R² and R³ each represents ahydrogen atom; an alkyl, alkenyl or cycloalkyl group which has 12 orless carbon atoms and may substituted by at least one group selectedfrom hydroxy group, amino group which may be substituted by at least onealkyl group and C₁₋₆ alkoxy group; an acyl group having 12 or lesscarbon atoms; an alkylsulfonyl group having 12 or less carbon atoms; ora phenylsulfonyl group which may be substituted by at least one alkylgroup; or R² and R³ may form a 4- to 7-membered ring cyclic amino grouptogether with a nitrogen atom adjacent thereto, R⁴, R⁵ and R⁶ eachrepresents a hydrogen atom; a hydroxy group; an amino group; an alkylether group; or an alkyl or alkenyl group which has 12 or less carbonatoms and may be substituted by at least one group selected from ahydroxy group, and an amino group which may be substituted by at leastone alkyl group, m stands for an integer of from 2 to 5, n stands for aninteger of from 1 to 4 and p stands for an integer of from 2 to 6, orsalt thereof, (b) an oxidizing agent; (c) an alkali agent; and (d) anintermediate for oxidation dye, or a direct dye; and has, after mixing,a pH of from 7.5 to
 12. 5. A hair dye composition to be used aftermixing a first component part containing an alkali agent and a secondcomponent part containing an oxidizing agent, which comprises, aftermixing, the following components (A) and (b) to (d): (A) a nitrogenouscompound having a solubility parameter logP in octanol/water rangingfrom −1 to 4, and a hydrogen peroxide remaining ratio from 5 to 90%; orsalt of the compound, (b) an oxidizing agent; (c) an alkali agent; and(d) an intermediate for oxidation dye, or a direct dye; and has, aftermixing, a pH of from 7.5 to
 12. 6. The hair dye composition of claim 4or 5, further comprising ethylenediaminetetraacetic acid,ethylenediaminehydroxyethyltriacetic acid ordiethylenetriaminepentaacetic acid or salt thereof.
 7. A hair treatmentadditive which comprises a nitrogenous compound represented by thefollowing formula (1) or (2):

(wherein, one or two of As each represents CH₂ which may be substitutedby one or two selected from O, S and NH, R¹ represents a hydrogen atom;an alkyl, cycloalkyl or alkenyl group which has 12 or less carbon atomsand may be substituted by at least one group selected from a hydroxygroup, an amino group which may be substituted by at least one alkylgroup, an amide group which may be substituted by at least one alkylgroup, a C₁₋₆ (poly)alkoxy or benzyloxy group which may be substitutedby a hydroxy group or an amino group, a thioether group and an estergroup; an alkyl halide group; or a benzyl, pyridylmethyl or phenyl groupwhich may be substituted by at least one halogen atom; R² and R³ eachrepresents a hydrogen atom; an alkyl, alkenyl or cycloalkyl group whichhas 12 or less carbon atoms and may substituted by at least one groupselected from hydroxy group, amino group which may be substituted by atleast one alkyl group and C₁₋₆ alkoxy group; an acyl group having 12 orless carbon atoms; an alkylsulfonyl group having 12 or less carbonatoms; or a phenylsulfonyl group which may be substituted by at leastone alkyl group; or R² and R³ may form a 4- to 7-membered ring cyclicamino group together with a nitrogen atom adjacent thereto, R⁴, R⁵ andR⁶ each represents a hydrogen atom; a hydroxy group; an amino group; analkyl ether group; or an alkyl or alkenyl group which has 12 or lesscarbon atoms and may be substituted by at least one group selected froma hydroxy group, and an amino group which may be substituted by at leastone alkyl group, m stands for an integer of from 2 to 5, n stands for aninteger of from 1 to 4 and p stands for an integer of from 2 to 6); orsalt thereof.
 8. A hair treatment additive comprising a nitrogenouscompound having a solubility parameter logP value in octanol/waterranging from −1 to 4, and has a hydrogen peroxide remaining ratio offrom 5 to 90%, or salt thereof.